We investigated chemical transformations of a fluorinated free-base porphyrin, 5,10,15,20-tetrakis(4-fluorophenyl)-21,23H-porphyrin (2H-4FTPP) under a Au(111) surface confinement and including gold adatoms by using an experiment and density functional theory based first-principles calculations. Annealing of 2H-4FTPP led to cyclodehydrogenation of the molecule to a π-extended fused aromatic planar compound, 2H-4FPP, and metallation of the porphyrin ring by Au atoms to Au-4FPP complex. Noticeable lowering of bond-dissociation energies of the pyrrole's C-H bonds of the Au(111) supported molecule with respect to their values in the gas phase explained the observed on-surface planarization. Our findings also indicate that Au adatoms may catalyze cleavage of C-H/F bonds in temperature-initiated processes on Au surfaces. BDEs and explicit inclusion of Au adatoms helps to rationalize thermally induced chemical reactions on the respective surface.

Institute of Physics Academy of Sciences of the Czech Republic Prague Czech Republic

Regional Centre of Advanced Technologies and Materials Faculty of Science Palacký University Olomouc Czech Republic

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